HRSG-14 IAPWS Guidance Documents - Dooley

International Association for the
Properties of Water and Steam
IAPWS Cycle Chemistry

Guidance Documents for Combined
Cycle/HRSG Plants
Barry Dooley
IAPWS Executive Secretary
Canadian HRSG Forum

Oakville, Ontario
20th 22nd October 2014
The Members of IAPWS
Members
BIAPWS [Britain and Ireland] Canada
Czech Republic Germany
Japan Russia
USA
Scandinavia [Denmark, Finland, Norway, Sweden]
Associate Members
Argentina and Brazil France
Italy Switzerland
Australia New Zealand
Greece (South Africa)
IAPWS Working Groups (WG)
Thermophysical Properties of Water and
Steam, TPWS
- Established IAPWS area (1929) Steam Tables
Industrial Requirements and Solutions, IRS
- Steam turbine manufacturers worldwide are members
Subcommittee on Seawater, SCSW
- Formed in 2008/2009 to address global need
Physical Chemistry of Aqueous Solutions, PCAS
- Formed in 1990 to support power plant chemistry
Power Cycle Chemistry, PCC
- Technical Guidance Documents for all Generating Sources
Details of each WG are on website (www.IAPWS.org)

News & Highlights
16th ICPWS. Greenwich, London, September 2013

- 150 Papers on all aspects of water and steam
- 230 people from 29 countries
- 10 Sessions on fossil and nuclear plant chemistries including
FAC and amines, and geothermal
- Proceedings available from IMechE in London
2014 IAPWS Meetings in Russia (23rd 27th June)

- PPChem Paper Provides Highlights for Power Plant
Chemistry
- New Technical Guidance Document
- Corrosion Product Sampling and Analysis
IAPWS Technical Guidance Documents (TGD)
for Combined Cycle Plants
Procedures for the Measurement of Carryover of Boiler Water
and Steam (September 2008). This document includes the
procedures to measure carryover from drum boilers to assist in
preventing steam turbine failure/damage.
Instrumentation for monitoring and control of cycle chemistry

for the steam-water circuits of fossil-fired and combined-cycle
power plants (September 2012). This document includes a table
that can be used to determine the minimum key level of
instrumentation required for any fossil or combined cycle/HRSG
plant.
Volatile treatments for the steam-water circuits of fossil and

combined cycle / HRSG power plants (July 2010). This document
includes the basis for AVT and OT for all plants with customization
for plants with ACC and using ammonia and amines.
Freely available and downloadable on IAPWS website www.IAPWS.org

IAPWS Technical Guidance Documents (TGD)
for Combined Cycle Plants
Phosphate and NaOH treatments for the steam-water circuits of

fossil and combined cycle / HRSG power plants (Oct 2011). This
document includes the basis for selecting the optimum boiler/HSRG
evaporator water treatment for (phosphate and NaOH treatments)
for all drum plants including customization for plants with ACC.
Steam Purity for Turbine Operation (Sept 2013). This document

covers guidance for a wide range of turbines (fossil, nuclear,
industrial, geothermal, etc) and failure mechanisms. It includes
customizations for plants using amines and with carbon dioxide.
Corrosion Product Sampling and Analysis (May 2014). This

document covers the optimum procedures and techniques for
monitoring iron and copper. Includes a table of achievable iron
levels for all types of plants including ACC
Freely available and downloadable on IAPWS website www.IAPWS.org

Technical Guidance Document

Monitoring and Analyzing Total Iron and
Copper in Fossil and Combined Cycle
Plants
Developed with input from 21 countries
May 2014
7
Introduction and Rationale for
Corrosion Product Sampling (CPS)
Significant problems with reliable and effective

corrosion product sampling observed worldwide in
fossil & combined cycle gas turbine (CCGT) plants
Corrosion product levels critical to determining

effectiveness or otherwise of cycle chemistry
programs - Total Fe and Cu levels key aspects of
IAPWS cycle chemistry Technical Guidance
Documents (TGD)
Critical activity either not done at all or conducted

incorrectly
8
Issues with Corrosion Product Sampling as
a Repeat Cycle Chemistry Situation
1. Incorrect sample collection systems

Poor system design, insufficient flow rates, no
sample preservation etc.
2. Incorrect sampling methodology

Time of day rather than unit operation focused
3. Incorrect analytical method

Detection limit too high, soluble only
4. Failing to account for particulates

No sample digestion step
9
Highlights of New TGD
1. Sampling system design critical for CPS
turbulent flow in all aspects of system most
important aspect
2. Suggestions for Locations, Achievable Levels and

Optimum Techniques for Analysis
3. CPS is a periodic activity
4. CPS should be undertaken during constant unit

operating conditions rather than at a convenient
time of the day
5. Most common CPS problems are a lack of sample

digestion and analytical method with high DL
Sample Locations for Corrosion
Product Sampling
Fossil/CCGT/Cogeneration
All Plants:
Air Cooled Condenser (ACC) Outlet (if
installed)
Condensate Filter Outlet (if ACC installed)
Economizer Inlet
Fossil:
LP & HP Heater Drains
CCGT:
Feedwater
Drum
Cogeneration:
Process condensate return
11
Achievable Total Fe & Cu Levels
Different Plant Types/Optimized Chemistry
Feedwater
OT: Total Fe = < 1 g/kg
AVT: Total Fe = < 2 g/kg
AVT (Mixed): Total Fe & Cu = < 2 g/kg
HP/LP Heater Drains: Total Fe & Cu = < 10 g/kg
HRSG Evaporators/Drums
AVT/PT/CT: Total Fe = < 5 g/kg
Air -cooled Condenser (ACC)
ACC Outlet: Total Fe = < 10 g/kg
Post Condensate Filter: Total Fe = < 5 g/kg
Cogeneration Plants
Condensate Return: Total Fe = < 10 g/kg*
*Depends on cogen plant design and function
12
Sample Digestion
Sample digestion critical to ensure all particulates

are dissolved
Requires correct use of acid / heat / time

Thioglycolic at 90C or boiling nitric acid
ICPS filters require full digestion
Key step that is often overlooked or done

incorrectly
13
Analytical Methods
Suitable methods
Post sample digestion UV-Vis (Ferrozine) with a 5
cm cell - Fe only
Graphite Furnace Atomic Absorption spectrometry
(GF-AA) post sample digestion
Inductively coupled plasma mass spectrometry
(ICP-MS) post sample digestion
Key points are:

1.Full digestion for all samples required
2.Detection limit of < 2 g/kg required, lower the DL
the better
14
New IAPWS TGD for 2015
- Amendment of IAPWS TGD for Fast Start HRSGs

- Instrumentation
- Volatile Treatments (AVT and OT)
- PT and CT
- New IAPWS TGD on HRSG HP Evaporator Sampling

for Internal Deposit Determination
- New IAPWS TGD on Ensuring the Integrity and

Reliability of Demineralized Make-up Water Supply to
the Unit Cycle
- New series of Guidelines on Amines

- Neutralizing amines (2015)
- Filming amines (maybe 2015)
International Resource for all areas of
Water and Steam
Meeting Bookmarks:
Canadian HRSG Forum (CHF), Toronto, Canada

20th 22nd October 2014
Australasian HRSG Users Group (AHUG)

Brisbane, Australia 8th 10th December 2014
European HRSG Forum (EHF)

11th 13th May 2015. Munich, Germany
2015 IAPWS Annual Meetings in Stockholm, Sweden

28th June 3rd July 2015
Resources for all areas of water and
steam
Freely available and downloadable on IAPWS website

- www.IAPWS.org
Please give full attribution to IAPWS

Technical Guidance Document

Steam Purity for Turbine Operation
Developed with input from 21 countries including most major

steam turbine manufacturers
September 2013
Key Highlights of the
IAPWS Steam Purity TGD
For the first time in the world covers all steam turbines
Provides guidance and limits to protect the turbine
Some relaxations for boilers on PT (using only TSP)
Clear indication that the composition of proprietary
chemicals must be known
Guidance on CO2 and how CACE relaxation can be used
Proper interpretation of Degassed CACE
How any relaxation depends on the knowledge of Na
PT Phosphate Treatment
TSP Tri Sodium Phosphate
CACE Conductivity after cation exchange
Customization for Turbine Types:
Boilers using Phosphate Treatment
With drum boilers that use solid alkalizing agents it may be

difficult to meet the standard case Na limits in steam
because of carryover of boiler water.
Tri-sodium phosphate (TSP) is not known to be corrosive to
turbine materials. Relaxed Na limit in steam is possible.
Customized Na limit will depend on turbine inspection results
indicating which quantities lead to excessive turbine deposits.
Maximum allowance is up to a Na limit of < 5 g/kg
But no allowance is possible if other products than TSP are
used (Phosphate blends, NaOH, proprietary chemicals of
undisclosed composition)
Elevated Levels of Carbon Dioxide
Moderate concentrations of carbon dioxide do not

significantly influence turbine chemistry in alkalized steam.
A limited allowance to CACE (max 2 S/cm) can be applied in
systems with feedwater pH>8.5, and the absence of corrosive
anions like Cl and SO4 can be reasonably excluded:
Use of degassed CACE
Regular ion chromatography analysis
Always use on-line monitoring of Na
Organic Decomposition Products
Natural organic matter:

Will partly decompose to organic acids
No allowance to standard case CACE limits
Amines for feedwater treatment:
Will partly decompose to organic acids; depending on
temperature, some amine may pass into the steam and
neutralize or over-compensate the effect of the acid
Allowance on CACE is possible, but only under conditions:
The exact composition of the product must be known
The species of decomposition products must be known
The decomposition products will not decrease pH in the
liquid films in the turbine
Regular ion chromatography analysis
Always use on-line monitoring of Na

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International Association for the

Properties of Water and Steam

IAPWS Cycle Chemistry

Canadian HRSG Forum

Details of each WG are on website (www.IAPWS.org)

16th ICPWS. Greenwich, London, September 2013

2014 IAPWS Meetings in Russia (23rd 27th June)

Instrumentation for monitoring and control of cycle chemistry

Volatile treatments for the steam-water circuits of fossil and

Freely available and downloadable on IAPWS website www.IAPWS.org

Phosphate and NaOH treatments for the steam-water circuits of

Steam Purity for Turbine Operation (Sept 2013). This document

Corrosion Product Sampling and Analysis (May 2014). This

Freely available and downloadable on IAPWS website www.IAPWS.org

Technical Guidance Document

Significant problems with reliable and effective

Corrosion product levels critical to determining

Critical activity either not done at all or conducted

1. Incorrect sample collection systems

2. Incorrect sampling methodology

3. Incorrect analytical method

4. Failing to account for particulates

2. Suggestions for Locations, Achievable Levels and

3. CPS is a periodic activity

4. CPS should be undertaken during constant unit

5. Most common CPS problems are a lack of sample

Sample digestion critical to ensure all particulates

Requires correct use of acid / heat / time

ICPS filters require full digestion

Key step that is often overlooked or done

Key points are:

- Amendment of IAPWS TGD for Fast Start HRSGs

- New IAPWS TGD on HRSG HP Evaporator Sampling

- New IAPWS TGD on Ensuring the Integrity and

- New series of Guidelines on Amines

Canadian HRSG Forum (CHF), Toronto, Canada

Australasian HRSG Users Group (AHUG)

European HRSG Forum (EHF)

2015 IAPWS Annual Meetings in Stockholm, Sweden

Freely available and downloadable on IAPWS website

Please give full attribution to IAPWS

Technical Guidance Document

Developed with input from 21 countries including most major

With drum boilers that use solid alkalizing agents it may be

Moderate concentrations of carbon dioxide do not

Natural organic matter:

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